Boika



Patented Nov. 1, 1927.

UNITED STATES PATENT OFFICE.

JAMES P. PENNY, OF BUFFALO, YORK, ASSIGNOR TO NATIONAL ANILINE & CHEMICAL C0,, INC., 01 NEW YORK, N. Y., A. CORPORATION OF NEW YORK.

No Drawing.

This invention relates to the manufacture and production of new disazo dyes for wool suitable for afterchroming or for dyeing on mordanted wool. In combination with me- 5 tallic salts or compounds, they are also valuable for printing on cotton. The materials dyed or printed with the new dyestuffs, with or without the use of mordants, also form a part of the present invention.

The new disazo dyes of the present invention can be obtained by coupling one molecular proportion of a diazotized beta-naphthylamine disulfonic acid (as first component) with one molecular proportion oi a primary amine of the benzene series having a free para position (as middle component),

diazotizing the amino monazo compound thus obtained and coupling it with one molecular proportion of an ortho-hydroxycarboXylic acid of the benzene series (as end component). In carrying out the first coupling,

it is-o'lten advantageous to employ the middle component in the form of its N-methylomega-sulfonic acid (sodium salt) deriva tive nuncn so ona,

and subsequently eliminating the N-methylomega-suli'onic acid group before proceeding with the second diazotization' and coupling with the end component.

The new dyes are salts of an acid having thefollowing probable formula:

40 wherein R and R each represent a hydrocarbon radical of the benzene series and 0: represents a hydrogen atom which may be substituted by an alkoxy group such as DUI-I OCJL, etc. In the dried and pulverized state and in the shape of their sodium salts, they are yellow to orange to brown powders soluble in water giving orange to brown solutions which on the additlon of caustic soda turn to a deeper shade. They are soluble in concentrated sulfuric acid giving generally bluish-red to violet solutions, andthey dyewool from acid baths giving generally yellow to orangeshades which are DISAZO DYE.

trate the invention, but it is understood that the invention is not limited thereto. The parts are by weight. w Exampler3 h7 parts of the sodium salt of 2-naphthylamine-6.S-disulfonic acid is disazotized in the known manner with 6.9 parts of sodium nitrite, 30 parts of 20 Be. hydrochloric acid and 800 parts water at a temperature of about 0 to 5 C. When diazotization is complete, add crystallized sodiunracetate to the well-stirred solution until the solution is no longer acid toward Congo red test paper but is still acid toward litmus test paper.

The diazo solution thus obtained is then slowly added to a well-stirred solution of 23 parts of the sodium salt of the N -methylomega-sulfonic acid derivative of aniline (prepared in the known manner by condensing aniline with an equimolecular proportion of 'lormaldehyde-sodium bisulfite compound in aqueous solution) in 1000 parts water containing 15 parts of sodium acetate. After stirring the mixture for a short time, 10 parts of sodium carbonate in aqueous solution is added. When the coupling is finished,,25 parts of caustic soda are added, and the solution heated to about 90 C. until no formaldehyde is further evolved. 100 parts of common salt are then added, theagitated solution allowed to cool to room temperature, and the separated amino-monazo compound filtered off. If desired, it may be resludgeol in. a saturated salt solution and again filtered off. 45 parts of the aminomonazo compound thus produced are dissolved in 1000 parts of water and diazotized by means of 6.9 parts sodium nitrite and 30 parts of 20 Be: hydrochloric acid, and the diazo solution added to a solution of 15.2 parts salicylic acid in 300 parts water at about 0 to 3 C. containing 30 parts of sodium carbonate and 10 parts caustic soda. The coupling iscomplete when attest shows no diazo compound to be present. The dye stuff is salted out by the addition of common salt, filtered off, washed, pressed and dried.

used and dyestuffs having similar properties will be. produced. Also, in place otaniline. o and m-toluidine-,. p-Xylidine, oand in anisidine, lanethyl-Q-amino-l-niethoxybenzene, and other. primary amines of the benzene series; haying a tree para position i he used, and instead oi: salicylic acid, ale. and other homologues of salicylic :n be used. in most cases the dime- .Z naphthylanrine disullonic acids can :ectly combined with the primary Without the previous. preparation of the El ineth:l-omegasultonic acid e.,. the i rniaidehydebisulfite compound) derivaoi? the primary Lin-i116..- In some cases, however, it is advantageous to proceed by way of the formaldehydedisulfite com pound; tor example, when coupling into aniline, o.-toluidine or o-anisidine.

I claim: 1. Process of producing disazodyestufis wl 1: comprises couplingone molecular proportion or diazotized beta-naphthylainine dii titanic acid with one molecular proportion or: a primary amine oi the benzene series havinga tree paraposition, diazotizi ng the no-ano compound thus: obtained and coup;-

' a with one molecular proportion of an hydroxycarboxylic acid of the benzene thoseries; a

:2. Process otproducing a disazo dyestutl Wl ich comprises coupling one molecular propoi ion of diazotized Q-naphthylamine-B.8.- disulto-nie acid with onemolecular proportion olithe N-methyl-omega-sulfonic acid lSOaH)flH and in the dried state forms a light brown I ei-airs The dyestufl has the following probable for mula:

OO ONa derivative of aniline, subsequently eliminating the: Nanethyhomega-su1tonic acid group and diazotizing the amino azo compound thus obtained and coupling it with one molecular proportion or salicylic: acid.

S. ihS new products, the disazo. dyestuils being salts of an acid having the following proiziable formula:

wherein and R each represent a hydrocarbon radical of the benzene series, the azo bridges being attached in para-position in the radical R, and a2 represents a hydrogen atom which may be substituted by an alltoxy group,s1=1ch as OCIL, OC H etc; said dye stui'ls in the dry and pulverized state in the shape of their sodium salts beingyellow to orange to brown powders soluble in Water giving orange tov brown solutions, and soluble in sulfuric acid giving generally bluishred to violet solutions; dyeing wool from an acid bath yellow to orange shades which upon atter-chrolning upon the fiber produce orange to brown shades; and chrome printed 011 cotton produces orange to brown shades.

4 As new products, the d'isazo dyestuffs which in the free state correspond with the following general formula:

COOH yellowish-brown to reddish-brown powders soluble 111 water grvlng orange to reddish till orange solutions, and soluble in concentrated sulfuric acid giving violet to reddish-violet solutions; dyeing wool yellow to reddishyellow shades which on being after-chromed change to reddish-brown shades; and chrome HOaS HOIS/ being in the dried and pulverized state in the shape of its sodium salt a light brown powder soluble in water with an orange color which 011 the addition of caustic soda changes to a red, and soluble in concentrated sula chromium compound.

9. Material dyed with a disazo dyestuff of printed on cotton produce orange to reddisl1- brown shades.

6. As a new product, a disazo dye being an alkali metal salt of the acid having the following probable formula:

COO11 claim 5, said dyestufl being mordanted with a chromium compound.

10. Material dyed with the disazo dyestufi of claim 6.

11. Cotton chrome-printed with a disazo dyestutt of claim 3.

12. Cotton chrome-printed with a disazo dyestuif of claim 4.

13. Cotton chrome-printed with a disazo dyest-ufl of claim 5.

14. Material chrome-printed with the dis azo dyestufi' of claim 6.

In testimony whereof I atfix my signature.

JAMES P. PENNY. 

